Hydrogen in Aluminium Solubility, Characterisation and Removal

R. N. Chouhan

Contents
Principles of solubility and removal of hydrogen Sources of hydrogen Defects caused by presence of hydrogen

Detection of Hydrogen
Removal

Principles

Solubility
Hydrogen Precipitation Principles of hydrogen removal

Solubility
3H2O + 2Al 6H + Al2O3 the equilibrium reaction for dissolution of hydrogen in aluminium can be expressed as H2 (gas) [H] (metal) For above equation equilibrium constant K is given by
KH = [activity of hydrogen] (partial pressure of H2)1/2

Sieverts Law
If the dissolved gas is sufficiently dilute that it obeys Henrys law KH = [Wt%H] / PH21/2
This expression is called Sieverts Law

above expression can be simplified as

Log(wt%H) = - A/T + Log(PH2) + Constant

Empirical relationship for solubility of hydrogen

log CH = -2761/T + 2.768

log CH = -2580/T + 1.399

(L)
(S)

Where, CH represents cc of hydrogen gas/100 g of aluminium at 1 atm and T is the absolute temperature

Solubility of hydrogen in aluminium at 1 atm

2.5

Hydrogen (ml/100g)

1.5

0.5

0 400

500

600

700

800

900

Temperature (C)

Effects of other alloying elements

Ce, Li, Th, & Ti increases

Si, Cu, & Sn decreases, and Fe, & Cr have a marginal effect on solubility

Hydrogen Precipitation

Co = Cs Cl
= 0.05

Concentration gradient ahead of the solidification front

Gas nucleation
For a gas bubble to nucleate remain stable or grow the pressure inside the bubble must be equal to or exceed the sum of the hydrostatic pressure, the pressure of the atmosphere above molten metal and surface tension forces PH2 Ph + Pa + Surface Tension forces

Where PH2 = equilibrium pressure of hydrogen

Ph = hydrostatic pressure of metal Pa = atmospheric pressure

Gas nucleation

LG cos + SG = SL
cos = (SL -SG) /LG

Gaseous cap formed on a solid substrate is shown along with the various interfacial energies which act.

Gas pores nucleated due inclusion which is pushed ahead of the solid-liquid interface

Bubbles trapped between dendrite arms

Forces acting on existing bubble

P ext P int
r

Equilibrium pore size

For mechanical equilibrium it can be simplified as Pint Pext =2T/r where T = surface tension 1 N/m2 for aluminium

So if Pext = 0.1 atm =0.1 x105 N/m2 and neglecting Pext

r2T/ Pint 0.5 m

Spherical pores

Typical porosities

The principle of hydrogen removal

KH = [Wt%H] / PH21/2

Log(wt%H) = - A/T + Log(PH2) + Constant

Application of vacuum Gas purging

The principle of gas purging

Atmosphere

H2

P3>P2

H2

H2

P2>P1

H2

Movement of gas purge bubble

H2

P1>0

H2

Melt containing dissolved Hydrogen

H2

P1 = 0

H2

Sources of hydrogen
Furnace atmosphere, which contains water vapour in addition to some H2 Moisture from refractories, dirty skimmers, and other furnace tools Hydrated corrosion products, which form part of the charge, such as

Weathered ingot and scrap

Sources of hydrogen
Oil contaminated turnings, chips, or scrap Damp fluxes, and Oil and hydroxide coating on metallic sodium used for modifying Al Si alloys

Metal mould reaction

Metal turbulence, improper gating

Dissolved hydrogen in molten aluminium results in porosity, the size and shape of which is dependent on

Composition of the alloy, Its solidification characteristics Microstructural features Presence of porosity nucleation sites. Interdendritic porosity, which is encountered when hydrogen content is sufficiently high ( > 0.15 cc/100 g)

Defects caused by presence of hydrogen

Porosity Low toughness Inferior surface finish Lower weldability Leakage of pressurised castings in service Bright flakes in forgings SCC in Al-Zn-Mg-Cu alloys H2 embrittlement

Detection of Hydrogen
Various quantitative and semiquantitative methods for the measurement of the hydrogen content in aluminium and its alloys featuring various degrees of sophistication have been evolved. The choice of the appropriate technique is often difficult since it can be affected by several factors, viz. Stage of production, Speed of analysis, Detection range, Capital investment

Desired accuracy,
Ease of operation etc.

Techniques for Solid Samples

Vacuum Tin Fusion Vacuum Fusion Nitrogen carrier Fusion Hot Vacuum Subfusion Extraction

Vacuum Tin Fusion

The technique involves fusing of the aluminium alloy sample in a molten tin bath at about 500C and extraction of the hydrogen evolved during the fusion process is delivered into an evacuated vacuum system. Depending on the alloy and its solubility in tin, complete solution of the sample requires 1-1.5 hrs. The apparatus consists of a furnace section where the hydrogen is extracted, a section for collection and measurement of gas evolved from the sample and a section for the analysis of the collected gas . The collected gas is analysed for hydrogen with a mass spectrometer or by diffusion through a palladium tube heated to 600c. Its accuracy is 0.070.08 cc/100 g for pure aluminium

Vacuum Fusion
This technique involves melting the prepared solid sample in a thoroughly degassed boron nitride, graphite, or alumina crucible in a high vacuum (10-3). A rapid evaluation of gas occurs as the metal is melted. This reaches completion after 3-5 mins. The hydrogen evolved is extracted and separated from background gas by a palladium tube or by analysing with a mass spectrometer

Nitrogen carrier Fusion

The sample is placed in an outgassed graphite crucible in a silica (quartz) tube. The graphite crucible is baked out and degassed at a high temperature (~2000C) by induction heating for 3-5 mins. The inside of this tube is isolated from the ambient atmosphere by a flow of nitrogen. The sample is introduced into the crucible. During surface contamination removal the surface temperature of the sample is reported to be at 400C-480C for 60 seconds. The sample is allowed to cool down for 5 mins before commencement of the extraction. The system is sealed and the sample is melted by induction heating by raising the plate current and gas is extracted for 3-5 mins. Hydrogen is extracted by diffusion from the liquid sample into the nitrogen stream and is then detected by katharometer

Hot Vacuum Subfusion Extraction

A dry-machined cylindrical sample, is heated in an evacuated clear silica tube to a temperature below eutectic or solidus temperature, until a definite endpoint is obtained on the gas evolution or extraction curve recorded with a strip chart recorder via a Pirani, Baratron or ionization gauge. The extraction time varies from 1-2 hrs. When extraction is complete, the gas is subjected to a simple analytical test at constant volume with either the mass spectrometer or by heating the palladium tube to diffuse the hydrogen out.

Techniques for Molten Metal Samples

Straube-Pfeiffer (Vacuum Gas) Test

The Initial Bubble Test

Recirculating Gas Methods

Straube-Pfeiffer (Vacuum Gas) Test

The Initial Bubble Test

Sample of molten aluminium contained in an electrically heated crucible is placed in a closed chamber, and vacuum is gradually applied until the first bubble is observed at the molten metal surface. The pressure and temperature at which the first bubble appears are recorded. A nomograph relating pressure, temperature and hydrogen solubility of the alloy being tested is used to obtain the hydrogen content.

Recirculating Gas Methods

It operates on the principle of monitoring hydrogen activity developed in a small quantity of inert gas continuously recirculated through the molten metal under test until the gaseous hydrogen diffused into the purged gas bubble is in equilibrium with the solute hydrogen in the molten metal in accordance with Sieverts law. If the solubility of hydrogen in the alloy at a given temperature and pressure is known then hydrogen C content can be obtained from: C = STP + (Pi/P)1/2

ALCOA Telegas IITM Instrument

Different Recirculating Gas Methods

ALCOA Telegas IITM Instrument QRG Test Unit SLM Hydrogen Determinator

Sample preparation and handling

Preparation and handling of samples are very critical in hydrogen content determination because contamination of the sample is one of the principle sources of spurious hydrogen in the determination of the hydrogen content in the solid alloy samples. In majority of the cases, surface preparation determines the reproducibility of the test results and thus should be standardised Samples by dry turning for direct method to be prepared with caution and immediately tested. After 24 hrs remachining is required. For liquid samples (indirect method), preheated mould permitting rapid solidification with smooth feeding is required to prevent loss of hydrogen and formation of porosity

Removal
Various methods of removing H2 from melt exist such as gas purging, vacuum and flux degassing. The most common methods (fig. 9) rely on bubbling gases through the melt to carry H2 to the surface. The efficiency of this process depends mainly on the size of the bubble produced- small bubbles give better efficiency. The types of gases used can be split into two categories, reactive and inert.

Reactive gases
The gases react with the melt in various ways. They usually contain Cl2, Cl2 compounds or Cl2 mixtures e.g. Cl2 Ar with 50% Cl2 N2 with 10% Cl2 Freon Hexachloroethane

Mixture Mixture Compound Compound

Inert gases
Nitrogen or argon is used to remove hydrogen from the melt. There is much less removal of solid particles by floatation. Some removal of Na and Mg may occur but this process can be carried out after SrAl modification.

Different degassing techniques

Natural degassing Vacuum degassing Ultrasonic treatment Gas purging Tablet/Flux degassing

Gas purging

Rotary degassing

Tablet/Flux degassing

Comparison of degassing techniques

Rotary Degassing Bubble Size: 2-5 mm Dispersion: Very Good Efficiency: High Consistency: Good

Porous Plug Bubble Size: 2-10 mm Dispersion: Fairly Poor Efficiency: Med.-Good Consistency: Medium

Lance Degassing Bubble Size: 2-3 cm Dispersion: Poor Efficiency: Poor-Med Consistency: Poor-Med.

Tablet Degassing Bubble Size: Variable Dispersion: Poor Efficiency: Variable Consistency: Poor